PL183379B1 - Non-aqueous inks and coatings containing carbonaceous products - Google Patents

Abstract

A non-aqueous coating or ink composition having incorporated therein a modified carbon product comprising carbon having attached a substituted or unsubstituted aromatic group is described. Also described is a modified carbon product comprising carbon and an attached organic group having a) an aromatic group and b) at least one group of the formula SO2NR2 or SO2NR(COR) wherein R is independently hydrogen, a C1-C20 substituted or unsubstituted alkyl, a C3-C20 substituted or unsubstituted alkenyl, (C2-C4 alkyleneoxy)xR' or a substituted or unsubstituted aryl; R' is hydrogen, a C1-C20 substituted or unsubstituted alkyl, a C3-C20 substituted or unsubstituted alkenyl, C1-C20 substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; and x is from 1 to 40.

Description

The invention relates to a non-aqueous coating composition, to a non-aqueous inkjet composition and to a carbon product.

Non-aqueous coating compositions and non-aqueous inkjet compositions are used in many fields where aqueous media are unsuitable. For example, inks that are printed on hydrophobic non-porous materials such as metal, glass, or plastic must be quick-drying. Therefore, in compositions for this purpose, non-aqueous solvents such as ketones, esters, alcohols or hydrocarbons are often used instead of water. Ink compositions based on such solvents are widely used in the industrial labeling of cardboard boxes and various metal or plastic containers and their components. Specific examples include novel ink compositions and heat curable, glossy, offset ink compositions.

Some applications require inks and coatings to be water resistant. Therefore, resins are dissolved in the solvents of non-aqueous inkjet and coating compositions to make them water-resistant when dried. Such non-aqueous coatings are mainly used for the coating of automotive parts, especially metal and plastic.

According to the invention, the non-aqueous coating composition comprising the non-aqueous solvent and the pigment is characterized in that the pigment comprises a modified carbon product which is carbon with a substituted or unsubstituted aromatic group attached, the aromatic group being directly attached to the carbon. Preferably, this composition additionally comprises a color pigment other than carbon black as a pigment. Preferably the aromatic ring of the aromatic group is an aryl group or a heteroaryl group. Preferably the aromatic group is a group of formula AyAr- where

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Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl and triazinyl;

A is hydrogen, a functional group selected from the group consisting of R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR ₂ , SO ₂ NR (COR), NR (COR), CONR ₂ , NO ₂ , and N = NR 'or A is a linear, branched or cyclic hydrocarbon radical, substituted or unsubstituted with one or more groups of the recited functional groups;

R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R, or substituted or unsubstituted aryl;

R 'is hydrogen, C] -C ₂₀ substituted or unsubstituted alkyl, substituted or unsubstituted aryl;

R is hydrogen, C 1 -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂ substituted or unsubstituted alkenyl, C 1-8 substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; x is 1-40 and y is an integer 1-5 when Ar is phenyl, 1-7 when Ar is naphthyl, 1-9 when Ar is anthracenyl, phenanthrenyl or biphenyl or 1-4 when Ar is pyridinyl or 1 -2 when Ar is triazinyl.

The non-aqueous coating composition according to the invention is preferably characterized in that the aromatic group has a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR), where R is independently hydrogen, C] - C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R 'or substituted or unsubstituted aryl, R' is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C] -C ₂₀ substituted or unsubstituted alkanoyl, or substituted or unsubstituted aroyl; x is 1-40. Preferably the aromatic group is a pC ₆ H ₄ SO ₂ NH ₂ group or a pC ₆ -H ₄ SO ₂ NHC ₆ H ₁₃ group, a pC ₆ H ₄ SO ₂ NHCOCH ₃ group or a pC ₆ H ₄ SO ₂ NHCOC ₅ H _{n group} .

The non-aqueous coating composition of the invention is preferably characterized in that the carbon is carbon black, graphite, vitreous carbon, fine carbon, activated charcoal, activated carbon or mixtures thereof. More preferably it comprises carbon black as the carbon.

According to the invention, the non-aqueous inkjet composition containing the non-aqueous solvent and pigment is characterized in that a pigment is a modified carbon product which is carbon with a substituted or unsubstituted aromatic group attached, the aromatic group being directly attached to the carbon. Preferably, the pigment additionally comprises a color pigment other than carbon black. Preferably the aromatic ring of the aromatic group is an aryl group or a heteroaryl group. Preferably the aromatic group is a group of formula AyAr- where

Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl and triazinyl;

A is hydrogen, a functional group selected from the group consisting of R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR ₂ , SO ₂ NR (COR), NR (COR), CONR ₂ , NO ₂ and N = NR 'or A is a linear, branched or cyclic hydrocarbon radical, substituted or unsubstituted with one or more of the mentioned phthalic acid groups;

R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R *, or substituted or unsubstituted aryl;

R 'is hydrogen, C _r C ₂₀ substituted or unsubstituted alkyl, substituted or unsubstituted aryl;

R 'is hydrogen, C] -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; x is 1-40 and y is an integer 1-5 when Ar is phenyl, 1-7 when Ar is naphthyl, 1-9 when Ar is anthracenyl, phenanthrenyl or biphenyl, or 1-4 when Ar is pyridinyl or 1- 2 when Ar is triazinyl.

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The non-aqueous inkjet composition according to the invention is preferably characterized in that the aromatic group has a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR), where R is independently hydrogen, C] -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R ', or substituted or unsubstituted aryl; R 'is hydrogen, C ₁ -C ₆ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; x is 1-40. Preferably the aromatic group is a pC ₆ H ₄ SO ₂ NH ₂ group or a pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ group or a pC ₆ H ₄ SO ₂ NHCOCH ₃ group or a pC ₆ H ₄ SO ₂ NHCOC ₅ H _{n group} .

Preferably, the non-aqueous inkjet composition comprises carbon black, graphite, vitreous carbon, finely divided carbon, activated charcoal, activated carbon, or mixtures thereof. More preferably it comprises carbon black as the carbon.

According to the invention, the carbon-containing carbon product with an attached organic group is characterized in that it is a modified carbon product having a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR), where R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R ', or substituted or unsubstituted aryl; R 'is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C 1 -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; x is 1-40. Preferably, the carbon product according to the invention comprises carbon black, graphite, glassy carbon, finely divided carbon, activated charcoal, activated carbon or mixtures thereof as carbon. More preferably it comprises carbon black as the carbon. Preferably, in the carbon product according to the invention, the aromatic group is the pC ₆ H ₄ SO ₂ NH ₂ group or the pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ group or the pC ₆ H ₄ SO ₂ NHCOCH ₃ group or the pC ₆ H ₄ SO ₂ NHCOC _{5 group} H _n .

Thus, the present invention generally relates to non-aqueous coating compositions and to non-aqueous inkjet compositions containing a modified carbon product consisting of carbon having an attached, substituted or unsubstituted aromatic group. The carbon as used herein is capable of reacting with a diazonium salt to form the above-mentioned modified carbon product. The carbon can be crystalline or amorphous. Examples include, but are not limited to, graphite, carbon black, glassy carbon, and activated charcoal or activated carbon. The above-mentioned carbons are preferably finely divided; it is also possible to use mixtures of different types of coal.

The carbon as used herein is capable of reacting with a diazonium salt to form the above-mentioned modified carbon product. The carbon can be crystalline or amorphous. Examples include, but are not limited to, graphite, carbon black, glassy carbon, and activated charcoal or activated carbon. The above-mentioned carbons are preferably in finely divided form; it is also possible to use mixtures of different types of coal. A modified carbon product can be prepared by reacting carbon with a diazonium salt in a liquid reaction medium to attach at least one organic group to the carbon surface. The diazonium salt may contain an organic group to be attached to the carbon. A diazonium salt of the present invention is an organic compound containing one or more diazonium groups. Preferred reaction media include water, any water-containing medium, and any alcohol-containing medium. Water is most preferred. These modified carbon products in which carbon is soot and various methods of their production are the subject of United States invention application No. 08/356 660 entitled "Reaction of Carbon Black with Diazonium Salts, Resultant Carbon Black Products and Their Uses", filed on December 15, 1994 year and its partial continuation filed concurrently with this application, both of these disclosures are incorporated herein by reference. These modified carbon products where carbon is not

183 379 carbon black and various methods of making them are the subject of United States Patent Application No. 08/356 653, entitled "Reaction of Carbon Materials With Diazonium Salts and Resultant Carbon Products", filed December 15, 1994, which is also incorporated herein. as a literature reference.

To produce the above-mentioned carbon products, the diazonium salt only needs to be sufficiently stable to react with carbon. Thus, this reaction can be performed with some diazonium salts otherwise believed to be unstable and prone to decomposition. Some of the decomposition processes may compete with the reaction between carbon and the diazonium salt and may reduce the total amount of organic groups attached to the carbon. In addition, the reaction may be performed at elevated temperature, whereby many of the diazonium salts may be susceptible to decomposition. Elevated temperature may also increase the solubility of the diazonium salt in the reaction medium and facilitate process control. However, elevated temperatures may lead to some loss of the diazonium salt due to other degradation processes. The diazonium salts of the present invention can be generated in situ. It is preferred that the modified carbon products of the invention contain no by-products or salt.

Carbon black can react with the diazonium salt when present as a dilute, stirrable aqueous slurry, or in the presence of sufficient water to form carbon black pellets. If desired, the carbon black pellets may be made using conventional pelletizing techniques. Other carbons may react similarly with the diazonium salt. Furthermore, if a carbon other than soot is used to produce modified carbon products used in non-aqueous inks and coatings, preferably the carbon should be ground to a very small particle size prior to reacting with the diazonium salt to prevent undesirable precipitation in the inks and coatings.

The organic group can be an aliphatic group, an organic cyclic group, or an organic compound that has an aliphatic and cyclic part. As mentioned previously, the diazonium salt used for the reaction with carbon can be derived from primary amines having one of these groups and capable of forming, even temporarily, a diazonium salt. The organic group can be substituted or unsubstituted, branched or unbranched. Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids, and carbohydrates. Organic cyclic groups include, but are not limited to, alicyclic hydrocarbyl groups (e.g., cycloalkyl, cycloalkenyl), heterocyclic hydrocarbyl groups (e.g., pyrrolidinyl, pyrrolinyl, piperidinyl, morpholinyl, and the like), aryl groups (e.g., phenyl, naphthyl, anthracenyl, and the like), and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, triazinyl, indolyl, and the like). If the steric hindrance of the substituted organic group increases, the number of the organic groups attached to the carbon in the reaction between the diazonium salt and the carbon may decrease.

If the organic group is substituted, it may contain any functional group compatible with the formation of the diazonium salt. Preferred functional groups include, but are not limited to, R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR (COR), SO ₂ NR ₂ , NR (COR), CONR ₂ , NO ₂ and N = NR '. R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl (branched or unbranched), C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R, or substituted or unsubstituted aryl. R 'is independently hydrogen, C] -C ₂₀ substituted or unsubstituted alkyl (branched or unbranched), or substituted or unsubstituted aryl. R is hydrogen, C 1 -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl. The integer n ranges from 1-8 and preferably 2-4. The integer x ranges from 1-40 and preferably 2-25. The anion X- is a halogen or an anion derived from an inorganic or organic acid.

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A preferred organic group is the aromatic group of the formula AyAr- which corresponds to the primary amine of the formula AyArNH ₂ . In this formula, the variables are: Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl and triazinyl; A is an aromatic radical substituent independently selected from the preferred functional groups described above, or A is a linear, branched or cyclic hydrocarbon radical (preferably containing 1-20 carbons), unsubstituted or substituted with one or more of these functional groups; ay is an integer 1-5 when Ar is phenyl, 1-7 when Ar is naphthyl, 1-9 when Ar is anthracenyl, phenanthrenyl or biphenyl or 1-4 when Ar is pyridinyl or 1-2 when Ar is triazinyl. When A is a (C ₂ -C ₄ alkyleneoxy) _x R group, it is preferably a polyoxyethylene group, a polyoxypropylene group or a random or block mixture of both. Particularly preferred organic groups are those indicated in the examples below.

A preferred modified carbon product contains carbon and an aromatic group attached having a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR). Preferably, R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) xR ', or substituted or unsubstituted aryl; R is hydrogen, C 1 -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C 1 -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; ax ranges from 1-40. Particularly preferred organic groups include pC ₆ H ₄ SO ₂ NH ₂ , pC ₆ -H ₄ SO ₂ NHC ₆ H ₁₃ , pC ₆ H ₄ SO ₂ NHCOCH ₃ , pC ₆ H ₄ SO ₂ NHCOC ₅ H _n and pC ₆ H ₄ SO ₂ NHCOC ₆ H ₅ .

The above modified carbon products are useful in non-aqueous inkjet compositions. Thus, the invention provides an improved ink composition comprising a solvent and a modified carbon product having an attached, substituted or unsubstituted aromatic group. Other known ink additives may be incorporated into this ink composition.

In general, the ink consists of four basic components: (1) a dye or pigment, (2) a vehicle or varnish that acts as a carrier during printing, (3) additives to improve printability, drying and the like, and (4) solvents to correct viscosity , drying and compatibility with other ink components. A general discussion of the properties, methods of making and application of inks is given in The Printing Manual, 5th ed., R.H. Leach et al., Ed. (Chapman & Hall, 1993).

The modified carbon products of the invention may be incorporated into the ink composition, either in pre-dispersed or solid form, using standard techniques. The use of the modified carbon products according to the invention can provide significant benefit and cost reduction by reducing the milling steps generally applicable to conventional carbon materials such as carbon black. The modified carbon products of the present invention can also provide improved jetness.

As will be outlined in more detail below, the non-aqueous coating compositions and non-aqueous inkjet compositions of the present invention may exhibit improved optical properties.

The modified carbon products of the invention can also be used in non-aqueous coating compositions such as paints or finishing paints. Thus, the invention provides an improved coating composition comprising a solvent, a binder and a modified carbon product having a substituted or unsubstituted aromatic group attached to it. Other conventional additives may be included in the non-aqueous coating compositions.

The composition of the coating varies widely depending on the conditions and requirements of the end use. Generally, the coating systems contain up to 30 wt.% Carbon. The amount of resin can vary within wide limits, almost up to

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100%. Examples include acrylic, alkyd, urethane, epoxy, cellulose resins and the like. The amount of the solvent varies from 0 to 80%. Examples include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, polyalcohols, ketones, esters, and the like. Two other general classes of additives are fillers and modifiers. Examples of fillers are other color pigments, clays, talcs, silicas, and carbonates. Fillers can be added up to 60% depending on the requirements of the end use. Examples of modifiers are flow and leveling agents and biocides, generally added in an amount of less than 5%.

The modified carbon products of the invention may be incorporated into non-aqueous coating compositions, either in pre-dispersed or solid form, using standard techniques. As with non-aqueous inkjet compositions, the use of a modified carbon product having an attached, substituted or unsubstituted ink group can provide significant benefit and cost reduction by reducing the milling steps generally used with conventional carbon materials. The modified carbon products of the invention may also provide improved flux ability.

The following examples are illustrative only, and are not intended to limit the claims.

Unless otherwise stated, BET surfaces obtained according to ASTM D-4820 are used for area measurements. CTAB surfaces were prepared in accordance with ASTM-D3765. DBPA data was obtained in accordance with ASTM D-2414.

Example 1. Preparation of PEG 750 methyl ether methanesulfonate

This example describes the preparation of PEG 750 methyl ether sulphonate used in Example 2. To a mixture of poly (ethylene glycol) methyl ether 750 average molecular weight (PEG 750 methyl ether) (30.4 g) and 20 ml of methylene chloride is added under nitrogen atmosphere (6.42 g) of pyridine. After all materials had dissolved, methanesulfonyl chloride (6.42 g) was charged over 3 minutes. In order to complete the reaction, stirring is carried out for a minimum of 4 hours, but also 18-48 hours.

Then, it was diluted with 100 ml of methylene chloride and then washed with deionized water (D.I. water), dilute HCl, and sodium bicarbonate solution. The methylene chloride solution was dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure to give the product as an oil 31.01 g (92.3% of theory). Ή-NMR analysis indicated 82% purity.

Example 2. Preparation of PEG 750 methyl ether sulfanilamide

This example describes the preparation of the PEG 750 methyl ether sulfanilamide used in Examples 11, 12 and 30. Sulfanilamide (3.74 g), 85% potassium hydroxide (1.2 g) and 30 ml acetonitrile are mixed under a nitrogen atmosphere. The reaction mixture is then heated to 60-70 ° C, then a small amount of water (<1 ml) is added. After stirring for approximately one hour at 60-70 ° C, a solution of PEG 750 methyl ether methanesulfonate (15 g) in 15 ml of acetonitrile was introduced over 10 minutes, followed by stirring at 60-70 ° C for approximately 14 hours.

Thereafter, the cleft is removed under reduced pressure. The residual material was diluted with 75 ml of methylene chloride and washed with deionized water (D.I. water) followed by saturated sodium chloride solution. The methylene chloride solution was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to yield the product as an oil, 13.45 g (82% crude yield). 1 H-NMR analysis indicated 80% purity.

Example 3. Preparation of PEG 350 Methanesulfonate of Methanesulfonate

This example describes the preparation of the PEG 350 methyl ether methanesulfonate used in Example 4. The procedure is similar to Example 1, except that

Instead of PEG 750 methyl ether, an equimolar amount of polyethylene glycol methyl ether with an average molecular weight of 350 (14.21 g) is used. This procedure yielded 16.55 g of product (95% crude yield). -NMR analysis indicated 85% purity.

Example 4. Preparation of PEG 350 Methyl Ether Sulfanilamide

This example describes the preparation of PEG 350 methyl ether sulfanilamide used in Example 13. Sulfanilamide (2.41 g), 85% potassium hydroxide (0.78 g) and 20 ml acetonitrile are mixed under a nitrogen atmosphere. The reaction mixture is then heated to 60-70 ° C, then a small amount of water (<1 ml) is added. After stirring for about 1 hour at 60-70 ° C, a solution of PEG 350 methyl ether methanesulfonate (5 g) in 5 ml of acetonitrile was introduced over 5 minutes, followed by stirring at 60-70 ° C for at least 4 hours.

Thereafter, the pH of the mixture is adjusted to a value of about 5 with acetic acid, followed by the removal of the solvent under reduced pressure. The residual material was diluted with 75 mL of methylene chloride and washed with deionized water (D.I. water) followed by saturated sodium chloride solution. The methylene chloride solution was dried over anhydrous sodium sulfate, filtered to give the product as a gel after concentration under reduced pressure, 4.93 g (84% crude yield). Ή-NMR analysis indicated 68% purity.

Example 5. Polyoxyethylene cetyl ether methanesulfonate (2)

This example describes the preparation of polyoxyethylene (2) cetyl ether methanesulflonate used in Example 6. To a mixture of polyoxyethylene (2) cetyl ether (30.4 g) and 10 ml of methylene chloride, was added under nitrogen (4.78 g) pyridine. After all the materials had dissolved, methanesulfonyl chloride (3.80 g) was introduced. After 3 hours, the reaction mixture was diluted with 15 ml of methylene chloride and then stirred for 18 hours.

Thereafter, the reaction mixture was diluted with 50 ml of methylene chloride, then washed with denominated water (D.L water), dilute HCl, and dilute sodium hydroxide solution. The methylene chloride solution was dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure to yield 11.78 g of product (95% crude yield). 1 H-NMR analysis indicated 90% purity.

Example 6. Preparation of polyoxyethylene 'N-cetyl ether sulfanilamide (2)

This example describes the preparation of polyoxyethylene IN-cetyl ether sulfanilamide (2) used in Example 14. The sulfanilamide is mixed with 85% potassium hydroxide (0.66 g) under nitrogen atmosphere (2.0 g) and then diluted with with 15 ml of acetonitrile. The reaction mixture is then heated to 60-70 ° C, then approximately 3 drops D.L of water and tetrabutylammonium hydroxide (1.18 ml of a 1.0 M solution in methanol) are added. Then, stirring is carried out at 60-70 ° C for 22 hours.

Approximately 2 drops of acetic acid are then added to the reaction mixture, followed by removal of the solvent under reduced pressure. The residue was diluted with 95 ml of methylene chloride and washed with deionized water (D.L water) and then with saturated sodium chloride solution. The methylene chloride phase is dried over anhydrous sodium sulfate and filtered to give 4.19 g of product (88% crude yield) after concentration under reduced pressure. 'H-NMR analysis indicated 90% purity.

Example 7. Preparation of a carbon black product

A mixture of sulfanilamide (5.0 g), 14.4 mL of 6N HCl, and 25 mL of deionized water is heated if necessary to dissolve the sulfanilamide. Then, the solution is cooled in an ice-water bath. The slurry is prepared with 100 g of carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g in 400 ml of DI water, then, with stirring, cooled in an ice water bath. Thereafter, (2.2 g) of sodium nitrite was dissolved in about 20 ml of DL water, and this solution was then introduced into the sulfanilamide solution over several minutes.

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After 10-20 minutes at 0-5 ° C, the diazonium salt is added to the slurry of the carbon black in water. Gas evolution was evident in about 5 minutes. The slurry is removed from the ice bath and stirred until gas evolution has ceased. The product can be isolated either by evaporating the water under reduced pressure at about 110 ° C or in a laboratory oven at about 125 ° C. Alternatively, the product may be isolated by filtration under reduced pressure and washing with water to remove salts as by-products. The product has the pC ₆ H ₄ SO ₂ NH ₂ groups attached.

Example 8. Preparation of a carbon black product

The procedure is as in Example 7 except that an equimolar amount of acetylsulfanilamide sodium is used in place of the sulfanilamide. As a result, a product with attached groups pC ₆ H ₄ SO ₂ NHCOCH _{3 is} obtained.

Example 9. Preparation of a carbon black product

Proceeding as in Example 7, under neutral to basic conditions, a slight excess of concentrated ammonium hydroxide over the amount of HCl used, approximately 5%, is added to the carbon black water mixture in the diazonium salt formation step. (The carbon black treated in this way is somewhat more water-dispersible and should first be digested in a dilute HCl solution before isolation by filtration). The product had the pC ₆ H ₄ SO ₂ NH ₂ groups attached.

Example 10. Preparation of a carbon black product

Proceeding as in Example 8, under neutral to basic conditions, a slight excess of concentrated ammonium hydroxide over the amount of HCl used, approximately 5%, is added to the carbon black water mixture in the diazonium salt formation step. (The carbon black treated in this way is slightly more water-dispersible and should first be digested in a dilute HCl solution before isolation by filtration.) The result is a product with attached pC ₆ H ₄ SO ₂ NHCOCH _{3 groups} .

Example 11. Preparation of a carbon black product

The procedure is similar to that used in Example 7. To a solution of 13.1 g of PEG 750 methyl ether sulfanilamide from Example 2 in 100 ml of DI water, 3.6 ml of concentrated HCl are added, followed by washing with 50 ml of deionized water. Then, the solution is cooled in an ice-water bath. A suspension of 25 g carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g, in 100 mL of water, cooled in an ice water bath.

To prepare the diazonium salt, 1.00 g of sodium nitrite in 10 ml of DI water is added to the PEG 750 methyl ether sulfanylamide solution. To reduce the excess nitric acid (III), 0.14 g of sulfamic acid (0.1 eq) is added. This solution is divided into two equal parts. Then, one part is added to the aqueous slurry of the carbon black in water. Gas is evolved from the slurry and agitation is continued until gas evolution ceases, in this case the dry carbon black product is obtained by evaporation in a vacuum oven at 110 ° C resulting in 30.1 g (approximately 98 % of expected weight). This leads to a product with attached pC ₆ H ₄ SO ₂ NH (C ₂ H ₄ O) ₁₆ CH _{3 groups} .

Example 12 Manufacture of carbon black product

The procedure is similar to example 11, but with a reduced number of operations. In this case, the diazonium salt is prepared by treating 1.0 g of PEG 750 sulfanilamide (Example 2), 0.27 ml of concentrated HCl and 0.08 g of NaNO ₂ per 10 g of carbon black. This leads to a product with attached pC ₆ H ₄ SO ₂ NH (C ₂ H ₄ O) ₁₆ CH _{3 groups} .

Example 13. Preparation of a carbon black product

The procedure is similar to Example 11, with the scale being half the size and using a diazonium salt prepared from 3.66 g of PEG 350 sulfanilamide from Example 4, 1.82 ml of concentrated HCl and 0.50 g of NaNO ₂ . Half the amount of this solution is treated with 12.5 g of carbon black. This leads to a product with attached pC ₆ H ₄ SO ₂ NH (C ₂ H ₄ O) ₇ CH _{3 groups} .

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Example 14. Preparation of a carbon black product

This treatment was identical to that of Example 13, except that 3.52 g of polyethylene N-cetyl ether sulfanilamide (2) from Example 6 was used instead of PEG 350 sulfanilamide (2). This resulted in a product with the β- _C6 groups attached. H ₄ SO ₂ NFl (C ₂ H ₄ O) _{2 C 6} H ₃₃ .

Example 15. Preparation of a carbon black product

Black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g. A suspension of this carbon black was prepared by mixing 50 g of carbon black in 450 g of water. A solution of 0.85 g of NaNO ₂ in 4 g of cold water is slowly added to a solution of 0.94 g of aniline and 1.98 g of concentrated nitric acid in 5 g of water which has been cooled in an ice bath. As a result, benzenediazonium nitrate is produced. After stirring for 15 minutes, this mixture is introduced into the carbon black slurry. Evolution of gas bubbles is observed. After bubbling ceased, the product was collected by filtration, washed twice with water, and oven dried at 125 ° C. As a result, a carbon black product with attached phenyl groups is obtained.

Example 16. Preparation of a carbon black product

Black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g. A suspension of this carbon black was prepared by mixing 50 g of carbon black with 450 g of water. A solution of 5.12 g of NaNO ₂ in 15 g of cold water is slowly added to a solution of 1.40 g of p-pentidine and 1.98 g of concentrated nitric acid in 5 g of water, which has been cooled to an ice bath. As a result, 4-ethoxybenzenediazonium nitrate is produced. After stirring for 15 minutes, this mixture is introduced into the carbon black slurry. Evolution of gas bubbles is observed. After 30 minutes, the product was collected by filtration, washed twice with water and dried in an oven at 125 ° C. This results in a carbon black product with attached pC ₆ H ₄ OC ₂ H _{5 groups}

Example 17. Preparation of a carbon black product

Black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g. A suspension of this carbon black was prepared by mixing 50 g of carbon black with 450 g of water. A solution of 0.85 g of NaNO ₂ in 4 g of cold water is slowly added to a solution of 2.98 g of 4-tetradecylaniline, 1.98 g of concentrated nitric acid and 4 ml of acetone in 15 g of water which has been cooled in an ice bath . As a result, 4-tetradecylbenzenediazonium nitrate is produced. After stirring for 15 minutes, this mixture is introduced into the carbon black slurry. Evolution of gas bubbles is observed. After 30 minutes, the product was collected by filtration, washed with water and tetrahydrofuran (THF) and dried in an oven at 125 ° C. The result is a carbon black product had attached pC ₆ H ₄ C ₂₉ H _I4.

Example 18: Preparation of polyoxyethylene lauryl ether sulfanilamide (4)

This example describes the preparation of polyoxyethylene lauryl ether sulphanilamide (4) used in Examples 20 and 21. To a mixture (10 g) of polyoxyethylene lauryl ether (4) and 10 ml of methylene chloride, pyridine (4.37 g) is added under nitrogen atmosphere. . After all the materials had dissolved, methanesulfonyl chloride (3.48 g) was introduced and the temperature was kept below 40 ° C. After about 1 hour, the reaction mixture is diluted with 10 ml of methylene chloride and continued for 21 hours.

Thereafter, the reaction mixture was diluted with 50 mL of methylene chloride and then washed with deionized water (D.I. water), dilute HCl solution, and dilute sodium hydroxide solution. The methylene chloride solution was dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure to yield 10.49 g of product (86% crude yield). 'J-NMR analysis indicated 83% purity. This product, polyoxyethylene (4) lauryl ether methanesulfonate, was used according to the procedure below.

Sulfanilamide (1.88 g), 85% potassium hydroxide (0.61 g) were mixed under nitrogen atmosphere and then diluted with 15 ml of acetonitrile. The reaction mixture is then heated to 60-70 ° C, then about 3 drops of deionized water and tetrabutylammonium hydroxide (1.1 ml of a 1.0 M solution in methanol) are added and (4.0 g) is added. polyoxyethylene (4) cetyl ether methanesulfonate, dissolved

183 379 in 5 ml of acetonitrile. Stirring is carried out for 22 hours at a temperature of 60-70 ° C. After 3 hours, additional acetonitrile (20 ml) was introduced.

Then, 6 drops of acetic acid are added, followed by removal of the solvent under reduced pressure. The residue was diluted with 75 ml of methylene chloride and washed with deionized water (D.L water) followed by saturated sodium chloride solution. The methylene chloride phase was dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure to give 4.27 g of the product (91% crude yield). Ή-NMR analysis indicated 88% purity.

Example 19. Preparation of 'Hexylsulfanilamide

This example describes the preparation of the N-Hexylsulfanilamide used in Examples 22 and 23. Sulfanilamide (10 g) is mixed with 85% potassium hydroxide (2.79 g) under a nitrogen atmosphere and then diluted with 100 ml of acetonitrile. The reaction mixture was then heated to 60-70 ° C and tetrabythylammonium hydroxide (5.6 mL of a 1.0 M solution in methanol) was added. N-hexyl bromide (9.12 g) is added to the reaction mixture, followed by washing with 20 ml of acetonitrile. Then it is stirred for 23 hours at a temperature of 60-70 ° C.

The solvent is removed under reduced pressure and the residue is diluted with 100 ml of ethyl acetate. This solution is washed with deionized water (D.L water) followed by a saturated sodium bicarbonate solution and a saturated sodium chloride solution. The ethyl acetate phase was dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure to yield 12.93 g of product (87% crude yield). After recrystallization from 50% aqueous ethanol solution, 9.90 g of product are obtained (69.8% of yield).

Example 20. Preparation of a carbon black product

Mixture (3.38 g) of polyoxyethylene lauryl ether sulfanilamide (4) from Example 18, 1.63 mL concentrated HCl), 10 mL of acetone and 50 mL of deionized water. This solution is then cooled in an ice bath. Prepare a suspension of carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g (11.25 g) in 50 ml DI 2ody with stirring and cooled in an ice water bath. 0.50 g of NaNO ₂ is dissolved in about 20 ml of deionized water, and this solution is added over a period of several minutes to the sulfanilamide solution.

After 10-20 minutes at 0-10 ° C, the diazonium salt solution is divided into two equal portions. One aliquot is added to the slurry of carbon black in water. Gas evolution is evident within approximately 5 minutes. The mixture is then removed from the ice bath and stirring continued until gas evolution ceases. The product was isolated by evaporating the water under reduced pressure at about 110 ° C. This results in a carbon black product with attached pC ₆ H ₄ SO ₂ NH (C ₂ H ₄ O) ₄ C ₁₂ H _{25 groups} .

Example 21. Preparation of a carbon black product in the presence of ammonium hydroxide

Suspension is prepared from (11.25 g) of carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g in a mixture of 0.68 mL concentrated ammonium hydroxide and 50 ml of deionized water, after which it is cooled on an ice water bath. Thereafter, the remainder of the diazonium solution from Example 20 was added to the slurry of the carbon black in water. Gas evolution was evident within 5 minutes. The slurry is removed from the ice bath and stirred until gas evolution has ceased. The product is isolated by evaporating the water under reduced pressure at about 110 ° C. The product was obtained with attached groups pC ₆ H ₄ SO ₂ NH (C ₂ H ₄ O) ₄ C ₁₂ H ₂₅ .

Example 22. Preparation of carbon black product

The Ν'-hexylsulfanilamide from Example 19 (7.43 g), 7.2 ml of concentrated HCl, 20 ml of acetone and 100 ml of deionized water are mixed and the solution is cooled in an ice-water bath. Prepare a suspension of carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g (50 g) in 200 mol of deionized water, after which it is cooled on an ice water bath. Sodium nitrite (2.20 g) was dissolved in approximately 20 mL of water and this solution was added over several minutes to the sulfanilamide solution.

After about 10-20 minutes at 0-10 ° C, the diazonium salt is treated with 0.28 g of sulfamic acid and divided into two equal portions. After adding one portion to a slurry of carbon black in water, gas evolution was evident in about 5 minutes. The slurry is removed from the ice bath and stirred until gas evolution has ceased. The product was isolated by filtration and then washed with several portions of deionized water. The wet solid is dried in vacuo at about 110 ° C. A product with attached groups pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ is obtained.

Example 23. Preparation of a carbon black product in the presence of ammonium hydroxide

Prepare a suspension of carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g (50 g) in a mixture of 3.0 mL concentrated ammonium hydroxide and 200 ml of deionized water, after which it is cooled on an ice water bath. The remainder of the diazonium solution from Example 22 was then added to the slurry of the carbon black in water. Gas evolution was evident within 5 minutes. The slurry is removed from the ice bath and stirred until gas evolution has ceased. The product was isolated by filtration and then washed with several portions of deionized water. The wet solid is dried in vacuo at about 110 ° C. A product with attached groups pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ is obtained.

Example 24. Evaluation of Carbon Black Products in Glossy Ink Systems

The carbon black products of Examples 7-14 were evaluated on a standard heat curable glossy ink formulation made on a three roll mill.

The carbon black samples were prepared for grinding in a three-roll mill by hand mixing 15 g of the carbon black with 35 g of the milled masterbatch consisting of 9 parts LV-3427XL (heat curable ground carrier, Lawter International, Northbrook, IL) to 1 part MAGIESOL 47 oil. until the sample is completely wetted. The mixture was then milled in a Kenf three-roll mill at 70 ° F. The samples were mixed with an equal amount of the milled premix, then the fineness was assessed on the G-2 fineness measuring device of NIPRI production. Standards passed four times through the mill. Additional passes were used if the fineness gauge read more than 20. The final ink was produced by mixing the ground stock with the same weight amount of the milled masterbatch.

MAGIESOL is a registered trademark of oils available from Magie Brothers, Franklin Park, IL.

Optical properties were measured on 3 mil samples that were dried at 285 ° F for 3 minutes. A Hunter color measuring device was used after the L *, a * and b * data were measured. Optical density was measured with a MacBeth RD918 densimeter. The gloss was measured with a BYK Gardner 4527 gloss meter.

The data on the degree of refinement of the carbon black products of Examples 7-14 and the optical properties of the obtained inks are shown below. The numbers shown in the table for the fineness are given in microns as measured on the G-2 and indicate the level where 3 defective grains are detected by the measuring device.

These data indicate that all of the carbon black products described in Examples 7-14 can be used to make the inks. Most of the carbon black products of these Examples yield jetter ink (low L *), and some of these products disperse through the milling medium faster than standard carbon black. Improved dispersion speed and color quality are highly sought after properties in the printing industry.

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Degree of fragmentation

Coal type / Number of passes through the mill 1 2 3 4 5 6 Standard, untreated 50 40 31 11 and and Example 7 50 48 thirty 10 and and Example 8 50 46 26 8 and and Example 9 50 thirty 25 5 and and Example 10 50 50 13 0 and and Example 11 50 50 13 0 and and Example 12 50 50 23 6 and and Example 13 50 50 40 42 and and Example 14 50 37 25 9 and and

“Grinding was complete after 4 passes.

Optical properties

Coal from example # Optical density Gloss (60 °) Hunter color measuring device L * and* b * Standard, untreated 1.94 115 5.70 -0.46 -2.28 7 2.22 109 3.18 -0.30 -1.40 8 2.12 108 3.82 -0.28 -1.36 9 2.35 90 2.39 -0.23 -1.19 10 2.07 110 4.45 -0.39 -1.62 11 2.25 114 3.05 -0.26 -0.96 12 1.99 113 5.15 -0.4- -2.13 13 2.26 113 3.13 -0.23 -1.10 14 2.18 100 3.58 -0.12 -0.30

Example 25. Evaluation of Carbon Black Products in Glossy Ink Systems

The carbon black products of Examples 15-17 were evaluated in the same glossy ink formulations as in Example 24, using the same procedures. The data in the tables indicate that the carbon black products obtained in Examples 15-17 can also be used in the preparation of inks.

Degree of fragmentation

Example / Number of passes through the mill 1 2 3 4 5 6 Standard, untreated 50+ 25 twenty 11 - - 15 50+ 36 31 twenty twenty 18 16 50+ 34 thirty 18 21 21 17 50+ 42 twenty 18 18 18

183 379

Optical properties

Coal from example # Optical density Gloss (60 °) Hunter color measuring device L * and* b * Standard, untreated 2.23 108 5.41 -0.34 -1.52 15 2.47 112 3.07 -0.25 -0.62 16 2.45 107 3.16 -0.18 -0.59 17 2.40 95 3.86 -0.42 -0.85

Example 26. Grinding data for Examples 20-23 from a three roll mill

The carbon black products of Examples 20-23 were evaluated in the same glossy ink formulations as in Example 24, using the same procedures. Examples 20-23 can also be used to make inks.

Degree of fragmentation

Example / Number of passes through the mill 1 2 3 4 5 6 twenty 50+ 34 23 twenty twenty 19 21 50+ 34 thirty 16 18 18 22 50+ 38 twenty 0 -and -and 23 50+ 24 28 22 11 8

“The grinding was stopped after 4 passes through the mill.

Optical properties

Coal from example # Optical density Gloss (60 °) Hunter color measuring device L * and* b * twenty 2.31 100 4.14 -0.02 -0.26 21 2.34 100 4.17 -0.07 -0.17 22 2.39 108 3.23 -0.38 -0.90 23 2.41 115 3.25 -0.35 -1.05

Example 27. Preparation of carbon black product

The sodium acetylsulfanilamide monohydrate (44.2 g) is mixed with 43.5 ml of concentrated HCl in 300 ml of deionized water. If necessary for deionized water. The mixture is heated, if necessary to dissolve the acetylsulfanilamide, and then cooled in an ice-water bath. In a separate trap, 50 g of carbon black with a surface area of CTAB 350 m ² / g and DBPA 120 ml / 100 g are slurried in 400 ml of deionized water, and then cooled in an ice-water bath. 6.6 g of sodium nitrite are dissolved in about 20 ml of DI water and this solution is added to the acetylsulfanilamide solution. After 10-20 minutes at 0-5 ° C, half of the diazonium salt solution was added to the slurry of the carbon black in water. Gas evolution was evident within 5 minutes. The slurry is removed from the ice bath and stirred until gas evolution has ceased. The product can be isolated, either by evaporating the water under reduced pressure at about 110 ° C or in a laboratory oven at 125 ° C. Alternatively, the product may be isolated by vacuum filtration and a water wash in

183 379 to remove salt by-products. After oven drying, it can be purified by Soxhlef extraction using 90% ethanol in water. This leads to a product with attached pC ₆ H ₄ SO ₂ NHCOCH _{3 groups} .

Example 28. Preparation of carbon black product

The procedure is similar to Example 27, except that the reaction is carried out under neutral to basic conditions, a slight excess of concentrated ammonium hydroxide over the amount of HCl used, approximately 5%, is added to the carbon black-water mixture during the diazonium salt formation step. . (The carbon black treated in this way is somewhat more water-dispersible and should first be reconstituted with a dilute HCI solution before isolation by filtration). The product had the pC ₆ H ₄ SO ₂ NHCOCH ₃ groups attached.

Example 29. Preparation of carbon black product

The procedure is similar to that of Example 28, except that in this example the sodium salt of acetylsulfanilamide was replaced with an equimolar amount of sulfanilamide. As a result, a product with attached pC ₆ H ₄ SO ₂ NH ₂ groups was obtained.

Example 30. The methodology for this example was similar to that of Example 28.

To a solution of 221 g of PEG 750 methyl ether sulfanilamide (from Example 2), 62% by weight, in 2.1 L of D.L water, 61 mL of concentrated HCl is added, followed by washing with 100 mL of deionized water. Then, the solution is cooled in an ice-water bath. To prepare the diazonium salt, a solution of 8.0 g (0.95 eq.) Sodium nitrite in 30 ml. Deionized water is added to this solution, followed by the addition of 2.2 g sulfamic acid (0.1 eq.) To reduce the excess nitric acid (III).

Prepared suspension of 50 g carbon black with a CTAB surface area of 350 m ² / g and a DBPA of 120 mL / lOOg, in a mixture of 450 ml of deionized water and 25.5 ml of concentrated ammonium hydroxide, then it is cooled on an ice water bath. Then, half of the diazonium solution is added to the carbon black slurry. Gas evolution was observed from the reaction mixture and was stirred until gas evolution ceased. In this case, the dry product was isolated by evaporating the water in a vacuum oven at 125 ° C and then extracted with a SoKhlef apparatus with 90% ethanol in water. This leads to a product with attached pC ₆ H ₄ SO ₂ NH (C ₂ H ₄ O) ₁₆ CH _{3 groups} .

Example 31. Preparation of carbon black product

Black with a CTAB surface area of 350 m ² / g and a DBPA of 120 ml / 100 g. A suspension of 50 g of this carbon black by stirring it with 450 g of water containing a few drops of isopropanol. A solution of 5.12 g of NaNO ₂ in 10 g of cold water is slowly added to a solution of 5.62 g of aniline and 11.88 g of concentrated nitric acid in 10 g of water which has been cooled in an ice bath. As a result of the reaction, benzenediazonium nitrate is formed. After stirring for 15 minutes, the reaction mixture was added to the carbon black slurry. Evolution of gas bubbles is observed. When the evolution of gas bubbles ceased, the product was isolated by filtration, washed twice with water and dried in an oven at 125 ° C to yield a product with attached phenyl groups.

Example 32. Preparation of carbon black product

Black with a CTAB surface area of 350 m ² / g and a DBPA of 120 ml / 100 g. A suspension of 50 g of this carbon black by stirring it with 450 g of water containing a few drops of isopropanol. A solution of 5.12 g of NaNO ₂ in 15 g of cold water is slowly added to a solution of 8.40 g of p-phenidine and 11.88 g of concentrated nitric acid in 10 g of water which has been cooled in an ice bath. As a result of the reaction, 4-ethoxybenzenediazonium nitrate is formed. After 15 minutes, the reaction mixture was added to the carbon black slurry. Evolution of gas bubbles is observed. When the evolution of gas bubbles ceased, the product separated into

By filtration, washed twice with water and dried in an oven at 125 ° C, obtaining a product with attached pC ₆ H ₄ OC ₂ H _{5 groups} .

Example 33. Preparation of carbon black product

Black with a CTAB surface area of 350 m ² / g and a DBPA of 120 ml / 100 g. A suspension of 50 g of this carbon black by stirring it with 450 g of water containing a few drops of isopropanol. A solution of 5.12 g of NaNO ₂ in 10 g of cold water is slowly added to a solution of 17.91 g of 4-tetradecylaniline, 11.88 g of concentrated nitric acid and 20 ml of acetone in 100 g of water which has been cooled in an ice bath . As a result of the reaction, tetradecylbenzenediazonium nitrate is formed. After stirring for 15 minutes, the reaction mixture was added to the carbon black slurry. Evolution of gas bubbles is observed. After stirring for 30 minutes, the product was isolated by filtration, washed with water and tetrahydrofuran (THF), then dried in an oven at 125 ° C to give a product with attached pC ₆ H ₄ C ₁₄ H _{29 groups} .

Example 34. Use of carbon black products in coating compositions

This example illustrates the use of carbon black products in thermosetting acrylic compositions. The surface treated with a carbon black with a CTAB surface 560 ^m2 / g and a DBPA of 100 ml / 100 g and carbon black with a CTAB surface 350 ^m2 / g and a DBPA of 120 mL / 100 g was used as the reference.

Coating compositions were prepared as follows. Each half-gallon steel mills is loaded with: 2.1 kg of 1/4 size steel balls, 3.3 kg of 1/2 size steel balls, 282 g of the ground masterbatch (64 parts of ACRYLOID AT 400 resin: 30 parts n-butanol: 6 parts methyl-n-amyl ketone) and 30 g of carbon black. The mill containers were rotated at 44 rpm on an 82 rpm apparatus (model 96806 Paul O. Abbe or similar) for the time indicated. The products were tested directly on the measuring device for measuring the fineness of Hegman at the indicated times. Grind values above 7 were generally taken as complete grinding. The data is presented below.

The final coating formulation was prepared by first reducing each fraction with 249 g of AT-400 resin, followed by turning for one hour. The second reduction was carried out by adding 304 g of a mixture consisting of 33 parts AT-400 resin, 35.3 parts CYMEL 303 melamine formaldehyde resin, 7.2 parts methyl n-amyl ketone; 8.5 parts of 2-ethoxyethyl acetate; 1.8 parts of CYCAT 4040 (acid catalyst consisting of toluenesulfonic acid and isopropylene); 0,3 parts of the additive FLUORAD FC 431; 14 parts of n-butanol followed by turning for one hour.

ACRYLOID is a registered trademark for resins available from Rohm & Haas, Philadelphia, PA. CYMEL and CYCAT are registered trademarks for products available from American Cyanamid, Stamford, CT. FLUORAD is a registered trademark for coating additives available from 3M, St. Paul, MN.

The optical properties were tested in a 3 mil film in a closed Lenet cuvette which was previously dried for 30 minutes and then heated for 30 minutes at 250 ° F. The data on the degree of grinding correspond to Hegman values, where the "sand" of the particles are grouped. The 'θ' value for sand means that there is sand throughout the entire measurement.

These data indicate that the carbon black products of Examples 27-33 can be used in acrylic thermosetting compositions. For the same grinding time, some of these products give better than standard coatings.

183 379

St. rozdr. 2h St. res. 4 h St. res. 6 h St. dissonance 23 h St. res. 25 h St. res. 48 h KU ^b Gloss L * and* b * Pow. after rev. standard. 4.2 5.5 6.2 7.2 7.2 nd ' 91 88 1.68 0.12 0.38 Pow. after rev. standard. ^and 4.4 4.0 ^c - - - 59h ^d 96 96 1.03 -0.07 -0.20 Not subjected to rev. standard. 4.8 5.2 ^C - - - 7.5 59 h 113 95 1.02 -0.10 -0.34 27 3 4 6.6 5 8+ na ^e 98 88 1.19 0.06 0.04 28 5 6 7.1 6.5 8+ na ^e 98 85 1.21 0.07 0.00 29 3 5.5 5.9 7.2 8+ n / a ° 98 90 1.23 0.00 0.04 thirty 3 4.5 5.4 8+ ___d na ^e 100 88 1.57 0.00 0.26 31 2.2 4.8 6.3 8+ 8+ n / a 92 91 1.58 0.09 0.26 32 3.2 3.8 3.5 ___d ___d ___d 88 91 1.00 -0.04 -0.12 33 1 1.1 0.9 2 2 5.5 ^f 89 92 1.43 0.09 0.30

^a Separate test with standard surface treatment for 59 h, with a limited number of samples.

^b Viscosity measured in Krebs Units on a KU-1 viscometer.

^c Samples were taken after 3 h.

^d Material is too sticky to measure.

^e Grinding is complete after 25 h.

The reading was taken after the first reduction.

Example 35. Use of carbon black products in coating compositions

This example illustrates the use of carbon black products in acrylic enamel compositions. Surface treated carbon black with a CTAB surface area of 560 m ² / g and a DBPA of 100 mL / 100 g was used as a reference. The carbon black products of Examples 32 and 33 were Soxhlef extracted with tetrahydrofuran before use.

The grinding is carried out in a paint shaker with a mixture of 200 g of 3/16 chrome steel balls, 2.19 g of the carbon black sample and a grinding medium consisting of 19.9 g of an 80/20 mixture, Acrylic Mixing Enamel DMR-499 [ PPG Finishes, Strongsvill, OH] and xylene. The total grinding time was 2 hours. The samples were evaluated with a Hegman measuring device at the time intervals listed below. At the end of the grinding cycle, the final composition is obtained by adding 23.3 g DMR-499, 17.3 g xylene, and 1.4 g DXR-80 urethane hardener [PPG Finishes, Strongsvill, OH] to each of the regrinds and shaking for additional 15 minutes.

3 mil samples of each formulation were made in a closed Lenet cuvette. The film was air-dried for 30 minutes and then heated at 140 ° F for 30 minutes. This film was used to evaluate the optical properties as shown below. The data on the degree of grinding correspond to Hegman's values, where the "sand" of the particles is clustered. The 'θ' values for sand mean that sand is present throughout the measurement. These data indicate that the carbon black products of Examples 29, 32 and 33 can be used to produce acrylic enamel compositions with good jetness.

Degree of fragmentation

Example / time (min) twenty thirty 40 50 * 60 70 90 120 Final lineup Pow. treated with soot 0.5 4.5 5 6+ 8 7.2 8 8 8 29 5.2 6 6.6 6.9 6.2 7 8 8 8 33 0.5 0 4 4.1 0.6 0.5 0.5 1.5 4.5 32 0 0 1 3.5 0.8 0.2 0.5 1.5 5.75

* Grinding was stopped after 18 hours and then restarted.

Optical properties

Example Gloss (60 °) Hunter color measuring device L * and* b * Not subjected to rev. standard. 92 0.59 -0.07 -0.28 29 95 0.39 -0.08 -0.18 33 88 0.88 -0.07 -0.09 32 73 1.63 -0.01 -0.12

Example 36. Preparation of N4 hexanoyl sulfanilamide

N, hexanoyl sulfanilamide is prepared as follows. Hexanoyl chloride (28.8 g) was added to a mixture of N ⁴ -acetylsulfanilamide (55.0 g and pyridine (54 ml) at 95 ° C over 20 minutes. An hour later, the reaction mixture was cooled to room temperature and diluted with with 600 mL D.L water, then acidified with aqueous HCl The product of this reaction N ⁴ -acetyl-N'-hexanoylsulfanilamide was isolated by filtration and washed with DI water (700 mL) to give an off-white solid. this is used directly in the next step.

The N ⁴ -acetyl-N'-hexanoyl sulfanilamide from the previous step is treated with sodium hydroxide (24.6 g) in DI water (200 mK1) while refluxing. After 3 hours of reaction, heating is discontinued and the pH of the solution is adjusted to 8 with 2N HCl. Then, the solution is cooled in an ice bath and then filtered to remove the sulfanilamide. The filtrate is acidified with aqueous HCl to a pH of 2 to precipitate the product Ν'-hexanoylsulfanilamide, 37.9 g. This product is recrystallized from hot ethanol (75 ml) and precipitated by adding 40 ml of DI water to the same. recrystallized process of Ν'-hexanoylosilanilamide in the amount of 24.8 g (43% of total yield). H ¹ NMR indicates a purity greater than 90%.

Example 37. Preparation of N ¹ , N * -bis (2-hydroxyethyl) sulfanilamide

N ', N ¹ -bis (2-hydroxyethyl) sulfanilamide is prepared as follows. This method was taken in part from G. DiModica and E. Angeletti, Gazz. Chim. Itak, 1960, 90, 434-9 [CA 55: 11344d]). Sodium carbonate (55.6 g), DI water (120 mL) and diethanolamine (57.8 g) were mixed and heated to 60-70 ° C. Then, acetylsulfanilyl chloride (116.8 g) as a solid was added over an hour. DI water (225 mL) was added portionwise while the acetylsulfanyl chloride was added to ensure stirring. Additional stirring is carried out for 3 hours at 60-70 ° C and then allowed to cool to room temperature over 16 hours. The solids are isolated by filtration and washing with 200 mL of cold DI water.

183 379

The crude product (170 g) was hydrolyzed for 4 hours with 5% NaOH solution (675 ml) at 60 ° C. The aqueous solution was extracted with three portions of ethyl acetate (1.5 L total). The extracts were dried over anhydrous sodium sulfate and then evaporated to give the product, N-N-Bisβ-hydroxyethylsulfanilamide, as an off-white solid, 72.1 g (55.5% crude yield) .

Example 38. Preparation of carbon black product

This example is an alternative method that does not require the addition of acid. Acetylsulfanilamide (10 g) is dissolved in 500 mL DI water at 90 ° C. To this solution was added (100 g) of carbon black with a surface area of 58 m ² / g and DBPA of 46 mL / lOOg. After the carbon black was introduced into the mixture, sodium nitrite (3.24 g) in DI water (10 ml) was added to the slurry. Gas evolution immediately began. Heating is discontinued and allowed to reach room temperature while stirring. The carbon black suspension is evaporated to dryness at 65 ° C. The result is a product with attached pC ₆ H ₄ SO ₂ NHCOCH _{3 groups} .

Example 39. Preparation of carbon black product

Sulfabenzamide (26.0 g), 23.5 ml concentrated HCl, 25 ml acetone and 100 ml water are mixed. A suspension of 58 m ² / g of a carbon black (100 g) and 46 ml / 100 g DBPA in 500 ml DI water was prepared and cooled in an ice-water bath with stirring. Sodium nitrite (6.50 g) is dissolved in approximately 25 mL DI water and this solution is added over a few minutes to the sulfabenzamide solution.

After 10-20 minutes, the diazonium salt solution is divided into two equal portions. One aliquot is added to the slurry of carbon black in water. Gas evolution begins immediately. The product was isolated by filtration and washed with DI water. The product was dried at 75 ° C for 16 hours. The product thus obtained had the pC ₆ H ₄ SO ₂ NHCOC ₆ H ₅ groups attached.

Example 40. Preparation of a carbon black product in the presence of ammonium hydroxide

Suspension is prepared from (100 g) of carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g in a mixture of 9.8 mL concentrated ammonium hydroxide and 500 ml dejonmizowanej water and stirred. The remainder of the diazonium solution from Example 39 was then added to the slurry of carbon black in water. Gas evolution was immediately observed. Stirring is continued until gas evolution has ceased. The product was isolated by filtration and washed with DI water. The product was dried at 75 ° C for 16 hours. The product thus obtained had the pC ₆ H ₄ SO ₂ NHCOC ₆ H ₅ groups attached.

Example 41. Preparation of carbon black product

Mix (12.7 g) of the Ν'-hexanoylsulfanilamide from Example 36 with 11.8 ml of concentrated HCl, 40 ml of acetone and 200 ml of DI water. Then, the solution is cooled in an ice-water bath. Prepare a suspension of (50 g) carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g in a mixture of 200 ml of deionized water with stirring and cooled in an ice water bath. Sodium nitrite (3.24 g) is dissolved in about 20 mL DI water, and this solution is added over several minutes to the N-hexanoyl sulfanilamide solution.

After 10-20 minutes at 0-10 ° C, the diazonium salt solution is split into two different portions. One aliquot is added to the slurry of carbon black in water. Gas evolution begins immediately. Thereafter, the suspension was removed from the ice bath and stirred until gas evolution ceased. The product is isolated by filtration and washing several times with water D. I. The wet solid is dried at 75 ° C. The product thus obtained had the P-C6H4SO2NHCOC5H]! Groups attached.

Example 42. Preparation of a carbon black product in the presence of ammonium hydroxide

Prepare a suspension of (50 g) carbon black with a surface area of 58 m ² / g and a DBPA of 46 ml / 100 g in a mixture of 4.9 mL concentrated ammonium hydroxide and 200 ml of deionized water with stirring and cooled in an ice water bath. The remainder of the diazonium solution from Example 41 was then added to the slurry of carbon black in water. Gas evolution was immediately observed. The slurry is then removed from the ice-water bath and stirred until gas evolution ceases. The product is isolated by filtration and washing

With several portions of DI water, the wet solid is dried at 75 ° C. The product thus obtained had the pC ₆ H ₄ SO ₂ NHCOC ₅ H _H groups attached.

Example 43. Preparation of carbon black product

Mix (66.3 g) of the N ¹ , N ¹ -bis (2-hydroxyethyl) sulfanilamide from Example 37 with 66.8 ml of concentrated HCl and 350 ml of DI water. Then, the solution is cooled in an ice-water bath. A suspension of carbon black (150 g) with a CTAB surface area of 350 m ² / g and a DBPA of 120 ml / 100 g is prepared in 1500 ml deionized water and cooled in an ice-water bath with stirring. Sodium nitrite (17.6 g) is dissolved in about 60 ml DI water, and this solution is added over a period of several minutes to the N ¹ , N ¹ -bis (2-hydroxyethyl) sulfanilamide solution.

After 10-20 minutes at 0-10 ° C, the diazonium salt solution is added one time to the slurry of carbon black in water. Gas evolution begins immediately. The slurry is then removed from the ice bath and stirred until gas evolution has ceased. The product is isolated by filtration and washing several times with water D. I. The wet solid is dried at 60 ° C. The product thus obtained had the pC ₆ H ₄ SO ₂ N (C ₂ H ₄ OH) ₂ groups attached.

Example 44. Preparation of carbon black product

In a solution of 340 ml of IN sodium hydroxide and 1700 ml of D.I water, sulfabenzamide (93.9 g) is dissolved. To this solution was added 200 g of carbon black with a CTAB surface area of 350 m ² / g and a DBPA of 120 ml / 100 g. After 15 minutes the slurry was added 85 ml of concentrated HC1. Sodium nitrite (23.5 g) is dissolved in approximately 75 mL DI water, and this solution is added over several minutes to the sulfabenzamide solution. Gas evolution begins immediately. The slurry is then removed from the ice bath and stirred until gas evolution has ceased. The product was isolated by filtration and washed several times with DI water. The wet solid was dried at 60 ° C. The product thus obtained had the pC ₆ H ₄ SO ₂ NHCOC ₆ H ₅ groups attached.

Example 45. The results of the grinding degree test for Examples 39-42 were obtained in a three roll mill

The carbon black products of Examples 39-42 were evaluated for absorption rate and optical properties according to the method described in Example 24. The data in the tables below indicate that the products of Examples 39-42 can be used in the preparation of ink. The products of Examples 39-42 show enhanced absorption by the grinding carrier.

Degree of fragmentation

Sample / Transition # 1 2 3 4 5 6 Not give up rev. standard 50 37 21 19 -and Example 39 50 48 32 thirty thirty 29 Example 40 50 46 thirty 22 twenty 22 Example 41 32 23 twenty twenty -and Example 42 twenty 22 twenty 18 -and

“The grinding was stopped after four passes through the mill.

The optical properties of the inks made with the carbon black products of Examples 39-42 and the untreated standard were determined from prints made using an RNA-52 printability tester (Research North America Inc.) and are shown in the table below. For 1.0 and 2.0 micron film, values were calculated from linear regression of overprint data having a range of film thickness.

183 379

Optical properties of the imprints of Examples 39-42

Processing the sample Film thickness (micron) Optical density L * and* b * Gloss @ 60 ° Not give up rev. standard 1.0 1.32 25.35 1.34 3.57 39.88 55 2.0 2.13 5.28 0.70 0.37 51.85 Example 39 1.0 1.15 30.91 1.60 4.88 34.98 55 2.0 1.85 10.59 1.28 2.59 47.52 Example 40 1.0 1.27 27.63 1.41 3.90 39.77 2.0 2.06 6.18 1.05 1.32 51.81 Example 41 1.0 1.31 25.30 1.55 4.28 37.92 55 2.0 2.01 8.02 0.91 1.17 45.43 Example 42 1.0 1.27 26.71 1.43 3.98 37.50 55 2.0 2.06 6.32 0.86 0.84 49.92

Example 46. Use of carbon black products in coating compositions

The carbon black products of Examples 43 and 44 were used in a thermosetting acrylic formulation as described in Example 34. The optical properties of these coatings obtained by ball grinding for 96 hours are summarized below. These data indicate that the carbon black products of Examples 43 and 44 can be used in the thermosetting acrylic composition.

Example L * and* b * Optical density ’ Gloss 60 ° KU Viscosity ^b 43 1.33 -0.01 -0.12 2.75 89.4 121 44 1.78 -0.01 -0.13 2.66 91.7 111

Optical densities were measured with the MacBeth RD918 density meter. ^b Viscosity was measured with Krebs Units on a Brookfield KU-1 viscometer.

183 379

Publishing Department of the UP RP. Mintage 60 copies. Price PLN 4.00.

Claims (30)

Patent claims 1. A non-aqueous coating composition comprising a non-aqueous solvent and a pigment wherein the pigment comprises a modified carbon product which is carbon with a substituted or unsubstituted aromatic group attached, the aromatic group being attached to the carbon directly. 2. A coating composition according to claim 1 The pigment of claim 1, wherein the pigment additionally comprises a color pigment other than carbon black. 3. A coating composition according to claim 1 The method of claim 1, wherein the aromatic ring of the aromatic group is an aryl group. 4. A coating composition according to claim 1 The method of claim 1, wherein the aromatic ring of the aromatic group is a heteroaryl group. 5. A coating composition according to claim 1 3. The aromatic group of claim 1, wherein the aromatic group is A _y Ar-, wherein Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridines! and triazinyl; A is hydrogen, a functional group selected from the group consisting of R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR ₂ , SO ₂ NR ₂ (COR), NR (COR), CONR ₂ , NO ₂ , and N = NR 'or A represents a linear, branched or cyclic hydrocarbon radical, substituted or unsubstituted with one or more groups of the recited functional groups; R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R, or substituted or unsubstituted aryl; R 'is hydrogen, C] -C ₂₀ substituted or unsubstituted alkyl, substituted or unsubstituted aryl; R is hydrogen, C 1 -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C 4 substituted or unsubstituted alkanoyl, or substituted or unsubstituted aroyl; x is 1-40 and y is an integer 1-5 when Ar is phenyl, 1-7 when Ar is naphthyl, 1-9 when Ar is anthracenes 1, phenanthrenyl or biphenyl or 1-4 when Ar is pyridines! or 1-2 when Ar is triazinyl. 6. A coating composition according to claim 1 3. The process of claim 1, wherein the aromatic group has a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR), where R is independently hydrogen, C ₁ -C ₁₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R 'or substituted or unsubstituted aryl, R' is hydrogen, C ₁ -C ₁₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C _R C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; x is 1-40. 7. A coating composition according to claim 1 6. The process according to claim 6, characterized in that the aromatic group is a pC ₆ H ₄ SO ₂ NH _{2 group} . 8. A coating composition according to claim 1 6. The process according to claim 6, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ . 9. The coating composition of claim 1 6. The process according to claim 6, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHCOCH ₃ . 10. The coating composition of Claim 6. The process according to claim 6, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHCOC ₅ H _n . 183 379 11. The coating composition of claim 1 The charcoal of claim 1, wherein the carbon is carbon black, graphite, glassy carbon, finely divided carbon, activated charcoal, activated carbon or mixtures thereof. 12. A coating composition according to claim 1. The carbon of claim 11, wherein the carbon is carbon black. 13. A non-aqueous inkjet composition containing the non-aqueous solvent and pigment wherein the pigment is a modified carbon product which is carbon with a substituted or unsubstituted aromatic group attached, the aromatic group directly attached to the carbon. 14. The ink composition according to claim 1, The pigment of claim 13, wherein the pigment is additionally a color pigment other than carbon black. 15. The ink composition according to claim 1, 13. The process of claim 13, wherein the aromatic ring of the aromatic group is an aryl group. 16. An ink composition according to claim 1, 13. The process of claim 13, wherein the aromatic ring of the aromatic group is a heteroaryl group. 17. An ink composition according to claim 1 13. The aromatic group of claim 13, wherein the aromatic group is a group of formula AyAr-, wherein Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl and triazinyl; A is hydrogen, a functional group selected from the group consisting of R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR ₂ , SO ₂ NR (COR), NR (COR), CONR ₂ , NO ₂ and N = NR 'or A represents a linear, branched or cyclic hydrocarbon radical, substituted or unsubstituted with one or more of the recited functional groups; R is independently hydrogen, C ₁ -C ₄ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R, or substituted or unsubstituted aryl; R 'is hydrogen, C-C ₂ o substituted or unsubstituted alkyl or substituted or unsubstituted aryl; R 'is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aroyl; x is 1-40 and y is an integer 1-5 when Ar is phenyl, 1-7 when Ar is naphthyl, 1-9 when Ar is anthracenyl, phenanthrenyl or biphenyl or 1-4 when Ar is pyridinyl or 1 -2 when Ar is triazinyl. 18. The ink composition according to claim 18 13. The process of claim 13, wherein the aromatic group has a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR), where R is independently hydrogen, C [-C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R ', or substituted or unsubstituted aryl; R 'is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, substituted or unsubstituted alkanoyl, or substituted or unsubstituted aroyl; x is 1-40. 19. An ink composition according to claim 1 17. A method according to claim 17, characterized in that the aromatic group is a pC ₆ H ₄ SO ₂ NH _{2 group} . 20. An ink composition according to claim 1 17, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ . 21. An ink composition according to claim 1 17, characterized in that the aromatic group is a pC ₆ H ₄ SO ₂ NHCOCH _{3 group} . 22. The ink composition of claim 1; 17, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHCOC ₅ H _n . 23. The ink composition according to claim 1, The carbon fiber of claim 13, wherein the carbon is carbon black, graphite, glassy carbon, highly ground activated carbon, charcoal, activated carbon, or mixtures thereof. 183 379 24. The ink composition according to claim 1, The carbon of claim 23, wherein the carbon is carbon black. 25. A carbon-containing carbon product with an attached organic group, characterized in that it is a modified carbon product having a) an aromatic group and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR), where R is independently hydrogen , C] -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R ', or substituted or unsubstituted aryl; R 'is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₁₀ substituted or unsubstituted alkanoyl, or substituted or unsubstituted aroyl; x is 1-40. 26. The carbon product of claim 26 A process as claimed in claim 25, characterized in that the carbon is carbon black, graphite, glassy carbon, finely divided carbon, activated charcoal, activated carbon or mixtures thereof. 27. The carbon product of claim 27 The carbon of claim 25, wherein the carbon is carbon black. 28. The carbon product of claim 28 27, characterized in that the aromatic group is a pC ₆ H ₄ SO ₂ NH _{2 group} . 29. The carbon product of claim 29 27, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ . 30. The carbon product of claim 30 27, characterized in that the aromatic group is a pC ₆ H ₄ SO ₂ NHCOCH _{3 group} . 21. The carbon product of claim 21 27, characterized in that the aromatic group is pC ₆ H ₄ SO ₂ NHCOC ₅ Hn. * * * This application is in part a continuation of United States Patent Application Nos. 08/356 462 and 08/356 653, filed December 15, 1994, the contents of which are hereby incorporated by reference.